CN110230103A - Zero dimension bismuthino perovskite monocrystal material and its preparation method and application - Google Patents
Zero dimension bismuthino perovskite monocrystal material and its preparation method and application Download PDFInfo
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- CN110230103A CN110230103A CN201910655644.7A CN201910655644A CN110230103A CN 110230103 A CN110230103 A CN 110230103A CN 201910655644 A CN201910655644 A CN 201910655644A CN 110230103 A CN110230103 A CN 110230103A
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- monocrystal material
- bismuthino
- perovskite monocrystal
- bismuthino perovskite
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
Abstract
The invention belongs to semiconductor optoelectronic field of detecting, and in particular to a kind of zero dimension bismuthino iodide R3Bi2I9Perovskite monocrystal material, the material (Bi2I9)3‑Unit is by organic ion R+It surrounds and then is formed dotted discontinuously arranged in three-dimensional space.The invention further relates to the application of the preparation method of the material and such material in X-ray detector.The present invention provides a kind of zero-dimension structural bismuthino perovskite monocrystalline new materials environmental-friendly, stability is high.Have benefited from the high stability of material, to advantages such as the highly attenuating coefficients of X-ray, it is only 182nGy to dosage rate that prepared detector radiation-resistant property is goodair s‑1X-ray with good signal respond, far below general medical diagnosis require 5.5 μ Gyair s‑1。
Description
Technical field
The present invention relates to a kind of X-ray detector materials and preparation method thereof, and in particular to a kind of R3Bi2I9Zero dimension bismuthino
Perovskite monocrystal material and its preparation method and application belongs to applying in X-ray detection field for novel perovskite material.
Background technique
X-ray radiates in environmental monitoring, safety inspection, Nuclear Science and Technology, medical imaging, industrial nondestructive testing, space
Many fields such as detection and high-energy physics are widely used.Nuclear radiation detector for X-ray detection is X-ray application process
In one of key technology, therefore continue to develop X-ray detection material and X-ray detection technology is current ray research field
Important development direction.
The third generation X-ray detector in phase early 1960s is risen, i.e., semiconductor detector has rings faster
Speed, stronger power spectrum resolution capability, broader energy linearity range and more compact system construction are answered, in accurate power spectrum
Measurement aspect is substantially better than gas ionization detector and scintillator detector.Especially Room-temperature Nuclear Radiation Detectors, it is simultaneous
Have cryogenic semiconductor detector high energy resolution and scintillator detector high detection efficient the advantages that, be very suitable for core section
, space science, medical imaging, safety inspection and environmental protection etc. are to detector quick response, high detection efficient, low detection
The multi-demands of lower limit, simply portable etc. properties.
Pb based perovskite material is applied to X-ray detection field for the first time within 2015.Hereafter, multinomial about halide perovskite
Material is applied to X, and the work of gamma-ray detection is registered successively.Document report result concentrates on three-dimensional Pb base halide perovskite
Material.There is the problems such as such as stability is poor, Pb is toxic in discovery during being applied to solar cell research of these materials, no
It is promoted the use of conducive to following commercialization.Meanwhile generally existing Ion transfer phenomenon in three-dimensional halide perovskite material, accordingly
Crystalline material resistivity relatively low (108-109Ωcm).The extra electric field that X-ray detector is applied when working is larger, applied electric field
Caused Ion transfer is unfavorable for the control of device creepage, causes the noise level of detector higher, limits detector spirit
The promotion of sensitivity.Meanwhile the Ion transfer phenomenon of extra electric field initiation is unfavorable for the long-time stability of device.
Compared with Pb, No. 83 bismuth (Bi) elements are a kind of relatively environment-friendly " green elements ", and Bi base halide being capable of shape
At the material of band gap~2.0eV perovskite structure, meet requirement of the room temperature X-ray detector to band gap；Its higher atom
Ordinal number is also advantageous to the absorption of X-ray.Studies have shown that relative to Pb base halide perovskite, Bi base halide perovskite
With better stability and weaker Ion transfer phenomenon.But, bismuthino perovskite material only has three-dimensional Cs at present2AgBiBr6
And two dimension (NH4)3Bi2I9For X-ray detection, further develops more novel B i based perovskite materials and be expected to as preparation height
Performance room temperature X-ray detector provides crucial material foundation.
Summary of the invention
That the purpose of the present invention is to provide a kind of environmental stabilities is higher, to the more sensitive novel bismuthino of X-ray detection
Perovskite monocrystalline new material.
The present invention is implemented as follows:
A kind of zero dimension bismuthino perovskite monocrystal material R3Bi2I9, (Bi2I9)3-Unit is by organic ion R+It surrounds and then is formed
It is dotted discontinuously arranged in three-dimensional space.
Wherein, organic ion R+ is CnH2n+1NH3 +(1≤n≤5), CnH2n+1C (=NH) NH2 +(0≤n≤5),
C6H5CnH2n+1NH3 +(1≤n≤4), C6H5CnH2n+1C (=NH) NH2 +One or more of (0≤n≤4) mixing.
The present invention also provides the preparation methods of bismuthino perovskite monocrystal material.
A kind of preparation method of bismuthino perovskite monocrystal material can add seed crystal progress using evaporation at constant temperature solvent method
Induced growth can not also add.If adding seed crystal, seed crystal is the tiny seed crystals for needing the target crystal grown, seed sized
Range is 0.1-5mm (optimum condition 0.5-3mm).
Crystal seed growth conditions: by BiI3(bismuth iodide) and RI (organic salt compounded of iodine) configure R3Bi2I9Precursor solution, solution are dense
Degree is 0.6M-2M (optimum condition 0.8-1.5M), and solvent can be GBL, DMF, one or more of DMSO.This is molten
Liquid is placed under 40 DEG C -200 DEG C (optimum condition is 50 DEG C -120 DEG C) isoperibols 0-150 hours, can be obtained seed crystal.
Crystal growth condition: by BiI3(bismuth iodide) and RI (organic salt compounded of iodine) configure R3Bi2I9Precursor solution, solution are dense
Degree is 0.6M-2M (optimum condition 0.8-1.5M), and solvent can be GBL, DMF, one or more of DMSO, adds seed
Crystalline substance does not add seed crystal, which is placed under 40 DEG C -200 DEG C (optimum condition is 50 DEG C -120 DEG C) isoperibols
Growth, can be obtained R3Bi2I9Monocrystal, crystal final size are decided by growth time and solute molal quantity.
The present invention also provides the applications of the bismuthino perovskite monocrystal material, are to be used to prepare X-ray detector.
Further scheme is:
The X-ray detector the preparation method is as follows:
Bismuthino perovskite monocrystal material is cut into the size of needs, in bismuthino perovskite monocrystal material both ends evaporation metal
X-ray detector has just been prepared in electrode.
Further scheme is:
The electrode material is gold, silver, copper, aluminium/graphite, conductive charcoal etc..
The X-ray detector being prepared is made of the electrode of bismuthino perovskite monocrystal material and its both ends.
Not only environmental-friendly the present invention provides a kind of bismuthino perovskite monocrystalline new material, stability is high, and prepare
X-ray detector detection is sensitive.In addition, the bismuthino perovskite monocrystalline new material of the application can be also used for preparing gamma-ray detection
The gamma ray detector of device, preparation has identical structure and similar functions with X-ray detector.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the X-ray detector that one embodiment of the invention is prepared；
Fig. 2 is the (CH that one embodiment of the invention is prepared3NH3)3Bi2I9Monocrystal sample；
Fig. 3 is the material phase analysis result data for the monocrystal that one embodiment of the invention is prepared；
Fig. 4 is based on (CH3NH3)3Bi2I9The X-ray response data of the X-ray detection device of monocrystal.
Fig. 5 is based on (CH3NH3)3Bi2I9Stability data of the X-ray detection device of monocrystal under x-ray irradiation.
Specific embodiment
The present invention is further illustrated in the following with reference to the drawings and specific embodiments.
Embodiment one
The preparation method for present embodiments providing zero dimension bismuthino perovskite monocrystal material, using evaporation at constant temperature solvent method, tool
Body are as follows:
By BiI3(bismuth iodide) and CH3NH3I (methylamino salt compounded of iodine) configures (CH3NH3)3Bi2I9Precursor solution, solution concentration
For 0.6M-2M (optimum condition 0.8-1.5M), solvent can be GBL, DMF, one or more of DMSO, add seed crystal
Or seed crystal is not added, which is placed in raw under 40 DEG C -200 DEG C (optimum condition is 50 DEG C -120 DEG C) isoperibols
It is long, it can be obtained (CH3NH3)3Bi2I9Monocrystal, crystal final size are decided by growth time and solute molal quantity.Wherein,
BiI3(bismuth iodide) could alternatively be BiX (halogenation bismuth), CH3NH3I (methylamino salt compounded of iodine) could alternatively be RX (organic halogen) use
In the similar zero dimension perovskite crystal of growth.
If selection addition seed crystal carries out induced growth, seed crystal is the tiny seed crystals for needing the target crystal grown, crystal seed
Size range is 0.1-5mm (optimum condition 0.5-3mm).
Wherein, seed crystal the preparation method is as follows:
By BiI3(bismuth iodide) and CH3NH3I (methylamine hydriodate) configures (CH3NH3)3Bi2I9Precursor solution, solution are dense
Degree is 0.6M-2M (optimum condition 0.8-1.5M), and solvent can be GBL, DMF, one or more of DMSO.This is molten
Liquid is placed under 40 DEG C -200 DEG C (optimum condition is 50 DEG C -120 DEG C) isoperibols 0-150 hours, can be obtained seed crystal.
The zero dimension bismuthino perovskite monocrystalline that the present embodiment is prepared is as shown in Fig. 2.Fig. 3 is the object phase point of counter sample
Result data is analysed, display material is (CH3NH3)3Bi2I9, hexagonal structure, category P63/mmc space group.Fig. 4 is based on (CH3NH3)3Bi2I9The X-ray response data of the X-ray detection device of monocrystal, in this embodiment it is possible to find out when x-ray source is opened
When, detector exports big current signal since resistance reduces, and when x-ray source is closed, detector restores just due to resistance
Initial value and export small current signal, detector to X-ray respond it is sensitive.It is worth noting that used x-ray source dosage
Rate is only 182nGyair s-1, far below 5.5 μ Gy of general medical diagnosis requirementair s-1.Fig. 5 is based on (CH3NH3)3Bi2I9
Stability test of the X-ray detection device of monocrystal under the irradiation of different x-ray dosage rate, the results showed that detector is higher
Performance is undamped after dosage rate and deposition large energy.
Embodiment two
The application for present embodiments providing bismuthino perovskite monocrystal material is to be used to prepare X-ray detector.
It is more specific:
The X-ray detector the preparation method is as follows:
Bismuthino perovskite monocrystal material is cut into the size of needs, in bismuthino perovskite monocrystal material both ends evaporation metal
X-ray detector has just been prepared in electrode.
The electrode material is gold, silver, copper, aluminium, graphite, conductive charcoal etc..
The X-ray detector being prepared, structure are as shown in Fig. 1.By bismuthino perovskite monocrystal material 2 and its two
The electrode 1,3 at end forms.
The high stability that has benefited from material, the highly attenuating coefficient to X-ray, the detector radiation-resistant property of preparation is good, right
Dosage rate is only 182nGyair s-1X-ray with good signal respond, far below general medical diagnosis require 5.5 μ
Gyair s-1。
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application
Within scope and spirit.
Claims (8)
1. a kind of zero dimension bismuthino perovskite monocrystal material, it is characterised in that: the material is R3Bi2I9, (Bi2I9)3-Unit is had
Machine ion R+It surrounds and then is formed dotted discontinuously arranged in three-dimensional space.
2. zero dimension bismuthino perovskite monocrystal material according to claim 1, it is characterised in that:
(Bi2I9)3-Organic ion R+ around unit is CnH2n+1NH3 +(1≤n≤5), CnH2n+1C (=NH) NH2 +(0≤n≤
5), C6H5CnH2n+1NH3 +(1≤n≤4), C6H5CnH2n+1C (=NH) NH2 +One or more of (0≤n≤4) mixing.
3. the preparation method of bismuthino perovskite monocrystal material as claimed in claim 1 or 2, it is characterised in that:
By bismuth iodide BiI3With organic salt compounded of iodine RI configure precursor solution, solution concentration 0.6M-2M, solvent GBL, DMF,
One or more of DMSO adds seed crystal or does not add seed crystal, which is placed in 40 DEG C of -200 DEG C of constant temperature
It being grown under environment, can be obtained the zero dimension bismuthino perovskite monocrystal material, crystal final size is decided by growth time, and
Solute molal quantity.
4. the preparation method of bismuthino perovskite monocrystal material according to claim 3, it is characterised in that:
The seed crystal seed sized range is 0.1-5mm；
Seed crystal the preparation method is as follows:
By bismuth iodide BiI3R is configured with organic salt compounded of iodine RI3Bi2I9Precursor solution, solution concentration 0.6M-2M, solvent GBL,
The solution is placed under 40 DEG C of -200 DEG C of isoperibols 0-150 hours, can be obtained by one or more of DMF, DMSO
Seed crystal.
5. according to the preparation method of the bismuthino perovskite monocrystal material of claim 3 or 4, it is characterised in that:
The precursor solution concentration is 0.8-1.5M, and isoperibol is 50 DEG C -120 DEG C, and seed crystal seed sized range is 0.5-
3mm。
6. the application of bismuthino perovskite monocrystal material as claimed in claim 1 or 2, it is characterised in that: be used to prepare X-ray detection
Device.
7. the application of bismuthino perovskite monocrystal material according to claim 6, it is characterised in that:
The method for preparing X-ray detector is as follows:
Bismuthino perovskite monocrystal material is cut into the size of needs, the evaporation metal electricity at bismuthino perovskite monocrystal material both ends
X-ray detector has just been prepared in pole.
8. the application of bismuthino perovskite monocrystal material according to claim 7, it is characterised in that:
The electrode material is gold, silver, copper, aluminium, graphite or conductive charcoal.
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| CN111816719A (en) * | 2019-09-24 | 2020-10-23 | 湖南大学 | All-inorganic halogen perovskite single crystal X-ray detector and preparation method thereof |
| CN113897681A (en) * | 2021-09-18 | 2022-01-07 | 湖北工业大学 | Preparation method of non-lead perovskite single crystal with (110) orientation |
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